Prof. G.V.
Ramana
Geotechnical and Geoenvironmental Engineering
Department of Civil Engineering
IIT/Delhi
Clay Chemistry
Clay minerals are composed of hydrous aluminum
silicates.
These minerals are generally made from stacks of two
types of sheets: silica tetrahedral sheets and alumina
octahedral sheets. These are rightly named as sheets,
because each is just a few angstroms thick and can be
thousands of angstroms wide in each of its
dimensions.
Each type of clay mineral family consists of stacks of
these elementary sheets in differing arrangements.
Clay Chemistry
Most minerals of interest to geotechnical engineers
are composed of oxygen and silicon—two of the most
abundant elements on earth.
Oxygen (92 vol% and 50 wt% of igneous rocks)
Silicon (0.8 vol% and 25 wt%)
Aluminum is also the next most common element in
clay soils’ composition.
Most clays are of platy formation (kaolinite, smectite
and illite).
Some with tubular or stringy shapes have also been
observed in nature (halloysite and attapulgite).
Clay Mineral Structures
The synthesis pattern for clays is:
Ions—molecules—sheets—layers—crystals.
Sheet upon sheet = layer, Layer upon layer = crystal.
The two basic units forming the clay minerals are:
Silicon tetrahedron and aluminum octahedron
The nature of the sheets and the manner in which
these layers are held together (interlayer bonding)
decides the fundamental crystalline structure for the
specific clay mineral, as well as the resulting overall
physical and chemical characteristics.
Silica Tetrahedron
(SiO4: one Si4+ surrounded by four O2-)
Tetrahedral sheets are bound by shared oxygens.
Alumina Octahedron
(AlO6 or Al(OH)6: one Al3+ surrounded by six O2- or
OH- ions).
Octahedral sheets are bound by shared oxygens.
These units bond chemically to form sheets of
tetrahedral units or octahedral units, and the sheets
also chemically bond to form layers of sheets.
Synthesis of Clay Minerals
Common Clay Minerals
Layering silica and alumina sheets together results in:
(1 silica : 1 alumina) clays
One octahedral sheet chemically bonded to one
tetrahedral sheet.
(2 silica : 1 alumina) clays
One octahedral sheet sandwiched between and
chemically bonded to two tetrahedral sheets.
The layers typically are held together by:
readily exchangeable cations (e.g. Na+, K+, Ca2+, Mg2+) or
intermolecular interactions (e.g. hydrogen bonding,
Van-der Waal’s bonding, dispersion forces).
1. Kaolinite
One of the most common clay minerals in
sedimentary and residual soils.
A unit sheet of kaolinite, which is approximately
0.7nm thick, is composed of one aluminum octahedral
layer and one silicon tetrahedral layer, joined together
by shared oxygens (a 1:1 Clay).
Kaolinite
Kaolinite is formed by the stacking of units with strong
hydrogen bonding between O2- and OH- of the tetrahedra
and octahedra, respectively.
Because of the strong bonding, kaolinite does not exhibit
swelling in water.
It is characterized by a low surface area (in the range of 5
– 15m2/g) and low CEC.
2. Illite
One of the most common clay minerals in stiff clays and
shale. Often present, sometimes interstratified with other
sheet silicates, in sedimentary and residual soil.
Illite is formed by two of sheets of silica and one sheet of
alumina, where successive layers are joined by potassium
ions (0.96m thick).
Illite
Weathering may remove intersheet K+ from the edges
of the plates.
Illite particles have terraced surfaces where one or
more unit sheets terminate, and have a specific
surface of 65 – 100m2/g.
3. Smectite
One of the most dominant clay mineral in some clays and
shales and in some residual soils derived from volcanic ash.
In montmorillonite, octahedral Al is partially replaced by
Mg atoms.
Large interlayer space because lacks strength of H-bonding
to hold layers together (Van-der Waals bond present).
Smectite
The bond between the layers is weak, thus, water
molecules enter between the voids and easily separate
the layers causing the clay to swell.
In a hydrous environment, water molecules penetrate
between the sheets and separate them by 1m (i.e.
four molecular layers of water).
Smectite
Number of water molecules and kinds of ions
determine thickness of interlayer space. Result is
shrinking and swelling (i.e. expanding clay).
Montmorillonite is most common among the
smectite family.
6. Halloycite
Halloysite is one of the most common minerals in residual
soils, particularly those from volcanic parent material.
It is a member of the kaolin subgroup of clay minerals. A
unit sheet of hydrated halloysite, including one molecular
layer of water, is approximately 1m thick (1:1 Clay).
A typical particle has the shape of a hollow tube or prism.
Clay Structure Summary
Kaolinite (1:1) Illite (2:1) Montmorillonite (2:1)
Non-expansive Non-expansive Highly expansive
Table 1: Summary of typical characteristics of dominant clay minerals
Mineral Kaolinite Illite Smectite Halloysite
Structure 1:1 2:1 2:1 1:1
Shape Platy Platy Platy Tubular
Isomorphous substitution Low Moderate High Moderate
CEC range (cmolc/kg) 3 – 10 10 – 40 80 – 150 40 – 50
Specific surface range
5 – 20 65 – 100 100 – 800 50 – 150
(m2/g)
Water sorption capacity Low Moderate High Moderate
Range of LL (%) 30 – 75 60 – 120 100 – 900 45 – 75
Range of PL (%) 25 – 40 35 – 60 50 – 100 10 – 25
Range of Activity < 0.5 0.5 – 1.0 1–7 0.5 – 1.0
Shrink/swell Negligible Low Very High (Non) swelling
Mineral Identification
Since the behavior of clays depends largely on their
fabric and mineralogy, it becomes essential to
distinguish and identify the different clay minerals.
Methods of identification:
X-Ray Diffraction Analysis (XRD)
Differential Thermal Analysis (DTA)
Electron Microscopy
Scanning Electron Microscopy (SEM)
Transmission Electron Microscopy (TEM)
Infrared Spectrometry
Illite Sodium Montmorillonite
Halloycite Attapulgite
Diffuse Double Layer (DDL)
There are a few water layers that remain with the
clay even when heated to oven temperatures of
100oC, which are called the adsorbed water layers.
Surrounding them are the layers less associated
with the clay, making up the rest of the highly-
viscous water layers.
The combination of
the exchangeable,
hydrated cations
and bound water on
the surface of clay
particles held in
place by the
electrical charge
deficiency in the
clay particles is
referred to
collectively as the
diffuse double layer
(DDL) or
electrostatic double
layer.
The adsorbed water is attached to the silicate mineral
surfaces by strong hydrogen bonds, thus making it
difficult to be removed.
Other processes such as ion hydration, osmotic
attraction and dipole attraction may also be prevalent
at the interface.
Because of the structure of a water molecule, the two
hydrogen atoms are located near one end of it and the
oxygen atom is found near the other end.
This causes the water molecule to act as a kind of bar
magnet, which is referred to as the bi-polar nature.
This phenomenon is what awards the water its peculiar
properties of fluidity and surface tension.
Diffuse Double Layer Thickness
1/ 2
1 0 DkT
DDL thickness =
2 2
K 2n0 e
D = dielectric constant, n0 = electrolyte
concentration, v = cation valence, T =
temperature (Kelvins), k = Boltzman’s constant, e
= electric charge.
Common thicknesses vary from less than 10 Å to
more than 400Å.
Specific Surface Area
Due to the small size of clay particles and their platy
formation, they exhibit high surface area to mass ratio
as compared to other soils.
This is known as specific surface area, measured in
square meters per gram of soil.
There are clays with specific surface areas of as high
as 800m2/g, meaning that only 12.5g of the soil have a
surface of a hectare.
The higher the specific surface area, it can be said
about the soil that electrostatic effect (i.e. colloidal
nature) is more dominant than gravity effect. Such a
property makes the clayey soils behave in manners
very different from other category soils.
2. Swelling/Shrinking
The main reason why clays are expansive starts
first with the inherent negative charges.
To balance the charge imbalance in the mineral
layers, cations and water molecules act together.
If there is insufficient water present to complete the
balance of charges, the soil will have a net negative
energy with the tendency to bring available water to
it, and the result being volume increase.
